CN107253965A - FRET molecule and its synthetic method of one class based on fluorine boron pyrroles and cumarin - Google Patents
FRET molecule and its synthetic method of one class based on fluorine boron pyrroles and cumarin Download PDFInfo
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- CN107253965A CN107253965A CN201710516982.3A CN201710516982A CN107253965A CN 107253965 A CN107253965 A CN 107253965A CN 201710516982 A CN201710516982 A CN 201710516982A CN 107253965 A CN107253965 A CN 107253965A
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- fret
- yellow solid
- fluorine boron
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- cumarin
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- 238000002866 fluorescence resonance energy transfer Methods 0.000 title claims abstract description 32
- FXURYRWDOBBQLX-UHFFFAOYSA-N N1C=CC=C1.[B].[F] Chemical class N1C=CC=C1.[B].[F] FXURYRWDOBBQLX-UHFFFAOYSA-N 0.000 title claims abstract description 15
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 title claims abstract description 10
- PQMOXTJVIYEOQL-UHFFFAOYSA-N Cumarin Natural products CC(C)=CCC1=C(O)C(C(=O)C(C)CC)=C(O)C2=C1OC(=O)C=C2CCC PQMOXTJVIYEOQL-UHFFFAOYSA-N 0.000 title claims abstract description 8
- FSOGIJPGPZWNGO-UHFFFAOYSA-N Meomammein Natural products CCC(C)C(=O)C1=C(O)C(CC=C(C)C)=C(O)C2=C1OC(=O)C=C2CCC FSOGIJPGPZWNGO-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 238000010189 synthetic method Methods 0.000 title claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 36
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000007787 solid Substances 0.000 claims abstract description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 238000004440 column chromatography Methods 0.000 claims abstract description 8
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims abstract description 4
- JKANAVGODYYCQF-UHFFFAOYSA-N prop-2-yn-1-amine Chemical compound NCC#C JKANAVGODYYCQF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims abstract description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000012265 solid product Substances 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910006124 SOCl2 Inorganic materials 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims 1
- 206010027145 Melanocytic naevus Diseases 0.000 claims 1
- 230000006837 decompression Effects 0.000 claims 1
- 238000001727 in vivo Methods 0.000 claims 1
- 229910052740 iodine Inorganic materials 0.000 claims 1
- 239000011630 iodine Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 229910021595 Copper(I) iodide Inorganic materials 0.000 abstract description 4
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 6
- 238000012546 transfer Methods 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 241000522215 Dipteryx odorata Species 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010226 confocal imaging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 125000006306 4-iodophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1I 0.000 description 1
- 206010006187 Breast cancer Diseases 0.000 description 1
- 208000026310 Breast neoplasm Diseases 0.000 description 1
- 101710094902 Legumin Proteins 0.000 description 1
- LIQLLTGUOSHGKY-UHFFFAOYSA-N [B].[F] Chemical compound [B].[F] LIQLLTGUOSHGKY-UHFFFAOYSA-N 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 125000000332 coumarinyl group Chemical group O1C(=O)C(=CC2=CC=CC=C12)* 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- BFMYDTVEBKDAKJ-UHFFFAOYSA-L disodium;(2',7'-dibromo-3',6'-dioxido-3-oxospiro[2-benzofuran-1,9'-xanthene]-4'-yl)mercury;hydrate Chemical compound O.[Na+].[Na+].O1C(=O)C2=CC=CC=C2C21C1=CC(Br)=C([O-])C([Hg])=C1OC1=C2C=C(Br)C([O-])=C1 BFMYDTVEBKDAKJ-UHFFFAOYSA-L 0.000 description 1
- NEKNNCABDXGBEN-UHFFFAOYSA-L disodium;4-(4-chloro-2-methylphenoxy)butanoate;4-(2,4-dichlorophenoxy)butanoate Chemical compound [Na+].[Na+].CC1=CC(Cl)=CC=C1OCCCC([O-])=O.[O-]C(=O)CCCOC1=CC=C(Cl)C=C1Cl NEKNNCABDXGBEN-UHFFFAOYSA-L 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 description 1
- 238000012921 fluorescence analysis Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- 239000000990 laser dye Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003068 molecular probe Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010048 yiguan Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/001—Preparation for luminescence or biological staining
- A61K49/0013—Luminescence
- A61K49/0017—Fluorescence in vivo
- A61K49/0019—Fluorescence in vivo characterised by the fluorescent group, e.g. oligomeric, polymeric or dendritic molecules
- A61K49/0021—Fluorescence in vivo characterised by the fluorescent group, e.g. oligomeric, polymeric or dendritic molecules the fluorescent group being a small organic molecule
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/001—Preparation for luminescence or biological staining
- A61K49/0013—Luminescence
- A61K49/0017—Fluorescence in vivo
- A61K49/0019—Fluorescence in vivo characterised by the fluorescent group, e.g. oligomeric, polymeric or dendritic molecules
- A61K49/0021—Fluorescence in vivo characterised by the fluorescent group, e.g. oligomeric, polymeric or dendritic molecules the fluorescent group being a small organic molecule
- A61K49/0039—Coumarin dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
- C09K2211/1055—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with other heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
Abstract
The present invention relates to FRET molecule and its synthetic method of the class based on fluorine boron pyrroles and cumarin.When prepared by the FRET molecules, first it is stirred at room temperature using coumaric acid as raw material in thionyl chloride and obtains yellow solid.Then in dichloromethane solution, yellow solid is further reacted with propargyl ammonia and triethylamine stirring at normal temperature, the product column chromatography for separation purification obtained after filtering obtains yellow solid.Further final goal compound is obtained with the reaction of fluorine boron pyrroles, cuprous iodide and palladium catalyst.The compound has preferably chemistry, photostability, with big stoke shift, it is adaptable to the fluoroscopic examination in organism, and autofluorescence in organism can be avoided to disturb.This class FRET molecules prepared by the present invention can be used for the fields such as life science and Supramolecular photochemistry, and application prospect is extensive.
Description
Technical field
The present invention relates to FRET molecule of the class based on cumarin and fluorine boron pyrroles's fluorogen.
Background technology
FRET (Fluorescence resonance energy transfer, FRET) refers to two
In individual different fluorogen, (it is generally less than when the distance between Spectral matching and two fluorogens is suitable), Ke Yiguan
The phenomenon that fluorescent energy is shifted from donor to acceptor is observed, i.e., when being excited with the excitation wavelength of donor, the glimmering of acceptor can be observed
Light is launched.If acceptor fluorescence quantum yield is zero, occurs energy transfer fluorescent and be quenched；If acceptor is also a kind of fluorescence
Emitter, then show the fluorescence of acceptor.Molecule with FRET is widely used at present, and it is that can be used for
Fluorescence molecule is detected, small to make up conventional fluorescent probe molecule stoke shift, is easily lacked by autofluorescence interference in organism
Fall into；The light trapping antenna that solar energy is converted into chemical energy can also be used as, because many fluorogens make its absorption spectrum significantly
Widen.FRET (FRET) molecule has manifested most important in the field such as life science and Supramolecular photochemistry
Irreplaceable effect.Accordingly, it is capable to which the exploitation for realizing the FRET molecules of FRET is the previous urgent need of mesh
Will.But build the molecule based on FRET (FRET) to be not easy to, on the one hand to consider fluorogenic donor and acceptor
Matching degree；On the other hand the connected mode and connection distance of two fluorogens are considered.
Fluorine boron pyrroles fluorochrome has very excellent photochemistry physical property, shows the following aspects：Tool
There is higher molar extinction coefficient；High fluorescence quantum yield；The spectral quality of dyestuff is highly stable, is not easily susceptible to solvent polarity
With the influence of pH value；The fluorescence spectrum peak width of dyestuff is narrower, so that dyestuff is detected more when analysis field is applied to
It is sensitive；Dyestuff has higher photostability, will not cause dyestuff knot because of the irradiation of stimulated luminescence during fluorescence analysis
The rapid light degradation of structure, so as to ensure that the change of spectral signal only comes from examined sample.These excellent properties cause
The fluorogen is swift and violent in the application development of organic functional material, turns into develop one of fluorogen of greatest concern at present.Tonka-bean
Element is due to special molecular structure, by the modification of diverse location substituent on coumarin ring, can obtain having difference
The absorption of scope and fluorescence emission wavelengths, so as to show different colours and the derivative with strong fluorescence, except being used as extensively
Outside fluorescent whitening agent, fluorescent dye and laser dye, because with preferable photoelectric properties, coumarin kind compound goes back quilt in the recent period
Applied to fields such as the fluorescence probes in organic photosensitive dyestuff and the bioprotein research of electroluminescent material solar cell.
Most important also most crucial part is exactly the selection of donor and acceptor, fluorogen fluorine boron in FRET
Pyrroles and the excellent photochemistry of cumarin and photophysical property cause it to be very suitable for the confession acceptor as FRET molecules, and fragrant
Legumin launch wavelength is in one relatively wide scope of 450-500 nanometers, and fluorine boron pyrroles fluorogen has just in this position
Strong absorption, therefore, finds a suitable connected mode and connection distance connects cumarin and fluorine boron pyrroles's fluorogen
To make it possible to achieve the efficient transfer of fluorescence resonance energy.
The content of the invention
The invention provides FRET molecule of the class based on fluorine boron pyrroles and cumarin, its general structure is such as shown in (I)：
Wherein, R=-H or
The second object of the present invention is to provide following method to realize：
A, 7- dimethylamino -2- oxygen -2H-3- coumaric acids are dissolved in SOCl2In solution.The reaction solution is protected in nitrogen
Under the conditions of be stirred at room temperature 3 hours.Filtering, ether washing precipitation, obtains yellow solid.Further processing is not immediately available for next step
Reaction.
B, the yellow solid for obtaining a steps are dissolved in dichloromethane solvent, add the propargyl ammonia of 1.1 times of moles
With the triethylamine of 2.2 times of moles, stirring at normal temperature, TLC determines reaction end, filtering, vacuum rotary steam.Column chromatography for separation obtains yellow
Solid product.
C, the yellow solid product for 1.2 times of moles that fluorine boron azole derivatives and b step are obtained, 0.05 times of mole
Cuprous iodide, dichloro two (triphenyl phosphorus) palladium of 0.02 times of mole be added to the in the mixed solvent of triethylamine and tetrahydrofuran,
Argon gas protects 40 DEG C of oil bath heating, after reacting 2 hours.Cooling, filtering, filter cake is repeatedly washed with dichloromethane, and merging filtrate subtracts
Pressure distillation.Gained solid uses column chromatography (distillate is dichloromethane), obtains target product.
Further, the volume ratio of both mixed solvents of triethylamine and tetrahydrofuran described in step c is 1:4.
Above-claimed cpd to prepare reaction equation as shown in Figure 1.
The FRET molecules of the present invention can be used for the fluorescent molecular probe to realizing fluoroscopic examination in organism, it is also possible to make too
The trapping molecule of solar ray energy, can there is wider absorption in absorption spectrum.
The feature that the FRET molecules of the present invention have is as follows：
The FRET molecules are excited under 400nm excitation wavelength, can be launched at 510nm green fluorescence or 620nm
Red fluorescence.Insensitive to solvent polarity, chemical stability is good.
The FRET molecules of the present invention are the molecules based on FRET, while comprising two kinds of fluorogens, wherein
One fluorogen as donor, a fluorogen as acceptor, the launch wavelength of donor and the absorbing wavelength energy of acceptor
In the range of matching somebody with somebody, and connected mode between two fluorogens and apart from moderate, when being possible to realize excited donor molecule, only
The fluorescence for having acceptor can be launched.Therefore, the realization key for synthesizing this FRET molecules is to need reasonable selection to supply acceptor fluorescence
Group, is allowed to collaboration matching, is possible to realize the transfer of fluorescence resonance energy.The present invention has synthesized collection fluorescein and fluorine boron pyrroles
The FRET molecules of two different chromophories, the molecule has preferably chemistry, photostability, can avoid cell or group
The interference for the autofluorescence knitted, it is small by solvent effect with big stoke shift；FRET molecules in the present invention are based on glimmering
Photoresonance energy transfer mechanism, by reasonable adjusting connected mode, matches the energy of two fluorogens, efficiently realizes fluorescence energy
Amount transfer.This quasi-molecule is suitable to biological vivo detection fluorescence probe, for the fields such as life science and Supramolecular photochemistry, application
Prospect is extensive.
Brief description of the drawings
Fig. 1 is FRET molecule syntheses route of the present invention.
Fig. 2 is that the embodiment of the present invention 1 prepares fluorescence molecule in MCF-7 (breast cancer cell) interior laser confocal imaging；
MCF-7 cells cultivate 30min with the fluorescence molecule of embodiment 1 (5 μM) normal temperature, are respectively 405nm, launch wavelength in excitation source
In 450 ± 15nm and 514 ± 15nm fluorescent emissions；
Wherein (a) is the overlapping of bright field and 514 ± 15nm fluorescent emissions；(b) it is 450 ± 15nm fluorescent emissions；(c) it is
514 ± 15nm fluorescent emissions；(d) MCF-7 cells are cultivated after 30min with the fluorescence molecule of embodiment 2 (5 μM) normal temperature, in bright field
Under picture.
Fig. 3 is that the embodiment of the present invention 2 prepares fluorescence molecule in the intracellular laser confocal imagings of MCF-7；MCF-7 cells are used
Cultivate 30min under embodiment 2 (5 μM) normal temperature, respectively excitation source be 405nm, launch wavelength 450 ± 15nm and 590 ±
25nm fluorescent emissions；
Wherein (a) bright field and 590 ± 25nm fluorescent emissions is overlapping；(b) it is 450 ± 15nm fluorescent emissions；(c) it is 590
± 25nm fluorescent emissions；(d) MCF-7 cells are cultivated after 30min with the fluorescence molecule of embodiment 2 (5 μM) normal temperature, under bright field
Picture.
Embodiment
Embodiment 1
The synthesis of a compounds 2 (7-N, N- dimethylamino -2- oxygen -2H-3- tonka-beans acyl chlorides)：7- dimethylaminos -2-
Oxygen -2H-3- coumaric acids (2.62g, 5mmol) are added to 20mL SOCl2In solution.Reaction solution room temperature under nitrogen protective condition
Stirring 3 hours.Filtering, ether washing precipitation, obtains yellow solid 2.13g, yield is 76%.It is used for next step immediately after anti-
Should.
B compounds 3：In the dichloromethane solution of 10 milliliters of compounds 2, addition propargyl ammonia (191mg,
0.848mmol, M=225) and triethylamine (248ml, 1.69mmol), stirring at normal temperature, TLC determines reaction end, filtered, and depressurizes
Revolving.Column chromatography for separation obtains yellow solid product.1HNMR(CDCl3) δ=9.00 (s, 1H, NH) .8.70 (s, 1H, ArH), 7.43
(d, 1H, J=8.8Hz, ArH), 6.65 (d, J=8.8Hz, ArH), 6.50 (s, 1H, ArH), 4.23 (s, 2H, CH2),3.46
(q, 4H, J=7.2Hz, CH2CH3), 2.25 (s, 1H, CH), 1.24 (t, 6H, J=7.2Hz, CH2CH3).TOF MS calcd
for C17H18N2O3 298.1317,found 298.1324
The synthesis of c compounds 4：By compound 3 (158mg, 0.53mmol), 8- (4- iodophenyls) fluorine boron pyrroles
(200mg, 0.44mmol), cuprous iodide (3.5mg, 0.022mmol), dichloro two (triphenyl phosphorus) palladium (6mg, 0.0086mmol)
It is added to the mixed solvent 5mL (v of triethylamine and tetrahydrofuran:V=1:4) in, argon gas 40 degree of oil bath heating of protection is reacted two hours
Afterwards.Cooling, filtering, filter cake is repeatedly washed with dichloromethane, merging filtrate, vacuum distillation.Gained solid, which is used column chromatography, (to be evaporated
Go out liquid for dichloromethane), obtain solid 169mg.Yield 62%.1HNMR(CDCl3) δ=9.10 (s, 1H, NH) .8.74 (s, 1H,
), ArH 7.57 (d, 2H, J=8.0Hz, ArH), 7.44 (d, 1H, J=9.2Hz, ArH), 7.23 (d, 2H, J=8.0Hz, ArH),
6.65 (d, 1H, J=9.2Hz, ArH), 5.98 (s, 2H, ArH), 4.50 (s, 2H, CH2), 3.46 (q, 4H, J=7.2Hz,
CH2CH3),2.55(s,1H,CH3),1.40(s,1H,CH3), 1.25 (t, 6H, J=7.2Hz, CH2CH3).TOF MS calcd
for C36H35BF2N4O3Na 643.2668,found 643.2653
Embodiment 2
By the compound (156mg, 0.53mmol, M=298) generated in example 1b and fluorine boron azole derivatives B-2 (275mg,
0.44mmol, M=626), cuprous iodide 3.5mg (0.022mmol), (triphenyl phosphorus) the palladium 6mg of dichloro two (0.0086mmol) in
The mixing of triethylamine and tetrahydrofuran is molten=agent 5mL (v:V=1:4) in, argon gas 40 degree of oil bath heating of protection is reacted two hours
Afterwards.Cooling, filtering, filter cake is repeatedly washed with dichloromethane, merging filtrate, vacuum distillation.Gained solid, which is used column chromatography, (to be evaporated
Go out liquid for dichloromethane), obtain solid 157mg.Yield 45%.TOF MS calcd for[C50H43BF2N4O3+Na]
819.3293,found 819.3250。
Claims (4)
1. FRET molecule of the class based on fluorine boron pyrroles and cumarin, it is characterised in that the structure with such as formula (I)：
Wherein, R=-H or
2. a kind of synthetic method of FRET molecules as claimed in claim 1, it is characterised in that comprise the following steps：
A, 7- dimethylamino -2- oxygen -2H-3- coumaric acids are dissolved in SOCl2In solution, room temperature is stirred under nitrogen protective condition
Mix 3 hours, filter, ether washing precipitation obtains yellow solid, further processing is not immediately available for next step reaction；
B, the yellow solid for obtaining a steps are dissolved in dichloromethane solvent, add 1.1 times of moles propargyl ammonia and
The triethylamine of 2.2 times of moles, stirring at normal temperature, TLC determines reaction end, filtering, vacuum rotary steam, and column chromatography for separation obtains yellow and consolidated
Body product；
C, the yellow solid product for 1.2 times of moles that fluorine boron azole derivatives and b step are obtained, the iodine of 0.05 times of mole
Change the in the mixed solvent that cuprous, 0.02 times of mole dichloro two (triphenyl phosphorus) palladium is added to triethylamine and tetrahydrofuran, argon gas
40 DEG C of oil bath heating is protected, after reacting 2 hours, is cooled down, filtering, filter cake is repeatedly washed with dichloromethane, merging filtrate, decompression is steamed
Evaporate, gained solid uses column chromatography (distillate is dichloromethane), obtains target product.
3. a kind of application of FRET molecules as claimed in claim 1 fluoroscopic examination in vivo.
4. a kind of FRET molecules as claimed in claim 1 trap the application on molecule in solar energy.
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